Methods for the preparation of cyclopentaoxasilinones and cyclopentaoxaborininones and their use

Abstract

In various aspects and embodiments the invention provides a method of preparing a cyclopentaoxasilinone, the method comprising contacting a siloxy-tethered 1,7-enyne with a thioether promoter. In another aspect, the invention provides a method of preparing a cyclopentaoxaborininone, the method comprising contacting a boronic ester-tethered 1,7-enyne with a thioether promoter.

What is claimed is: 
     
       1. A method of preparing a cyclopentaoxasilinone or cyclopentaoxaborininone, the method comprising contacting a siloxy-tethered 1,7-enyne or a boronic ester-tethered 1,7-enyne of Formula (Ia) or Formula (Ib) with a thioether promoter to form a cyclopentaoxasilinone or cyclopentaoxaborininone of Formula (II);
 wherein Formula (Ia) is as follows: 
 
       
         
           
           
               
               
           
         
       
       wherein
 E is Si or B ; 
 R 10a  and R 11a  are each independently selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, halogen, C 1 -C 6  alkoxy, C 6 -C 12  aryloxy, C 6 -C 12  aryl, C 4 -C 10  heteroaryl, trialkylsilane, hydroxy, halogen, nitrile, C(═O)OR 15a , and combinations thereof; 
 R 12a  is selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 6 -C 12  aryl, and combinations thereof; 
 R 13a  and R 14a  are each independently selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 1 -C 6  alkoxy, hydroxy and combinations thereof, wherein R 13a  and R 14a  may optionally fuse or join to form a ring; and 
 R 15a  is selected from the group consisting of hydrogen, deuterium, and C 1 -C 6  alkyl; 
 wherein Formula (Ib) is as follows: 
 
       
         
           
           
               
               
           
         
       
       wherein
 M +  is an alkali metal cation; 
 R 10b  and R 11b  are each independently selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, halogen, C 1 -C 6  alkoxy, C 6 -C 12  aryloxy, C 6 -C 12  aryl, C 4 -C 10  heteroaryl, trialkylsilane, hydroxy, halogen, nitrile, C(═O 0 )OR 15b , and combinations thereof; 
 R 12b  and R 13b  are each independently selected from the group consisting of C 1 -C 6  alkoxy, hydroxy, and combinations thereof, wherein R 12b  and R 13b  may optionally fuse or join to form a ring; 
 R 14b  is selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 6 -C 12  aryl, and combinations thereof; and 
 R 15b  is selected from the group consisting of hydrogen, deuterium, and C 1 -C 6  alkyl; 
 wherein Formula (II) is as follows: 
 
       
         
           
           
               
               
           
         
       
       wherein
    is 
 
       
         
           
           
               
               
           
         
         E is Si or B; 
         R 20  and R 21  are each independently selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, hydroxy, halogen, C 1 -C 6  alkoxy, nitrile, C 6 -C 12  aryloxy, C 6 -C 12  aryl, C 4 -C 10  heteroaryl, trialkylsilane, hydroxy, halogen, nitrile, C(=O)OR 27 , and combinations thereof; 
         R 22 , R 23 , and R 25  are each present or absent, valency permitting, and each R 22 , R 23 , and R 25  present is independently selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 1 -C 6  alkoxy, hydroxy, and combinations thereof; 
         R 24  and R 26  are each independently selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 6 -C 12  aryl, and combinations thereof; and 
         R 27  is selected from the group consisting of hydrogen, deuterium, and C 1 -C 6  alkyl; and 
         wherein when E in Formula (Ia) is Si the thioether promoter is 4-FBnSMe. 
       
     
     
       2. The method of  claim 1 , wherein the thioether promoter is isolated and reused. 
     
     
       3. The method of  claim 1 , wherein the thioether promoter is 4-FBnSMe. 
     
     
       4. The method of  claim 1 , wherein a first diastereomer of the cyclopentaoxasilinone or cyclopentaoxaborininone is formed with higher selectivity than a second diastereomer of the cyclopentaoxasilinone or cyclopentaoxaborininone. 
     
     
       5. The method of  claim 1 , wherein the step of contacting a siloxy-tethered 1,7-enyne or a boronic ester-tethered 1,7-enyne with a thioether promoter is by the step of contacting the siloxy-tethered 1,7-enyne or boronic ester-tethered 1,7-enyne with a transition metal carbonyl. 
     
     
       6. The method of  claim 5 , wherein the transition metal carbonyl is dicobalt octacarbonyl. 
     
     
       7. The method of  claim 1 , wherein the cyclopentaoxasilinone or cyclopentaoxaborininone of Formula (II) is a cyclopentaoxasilinone or cyclopentaoxaborininone of Formula (IIa) 
       
         
           
           
               
               
           
         
       
       wherein
 E is Si or B; 
 R 20a  is hydrogen or deuterium; 
 R 21a  selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, hydroxy, halogen, C 1 -C 6  alkoxy, nitrile, C 6 -C 12  aryloxy, C 6 -C 12  aryl, C 4 -C 10  heteroaryl, trialkylsilane, hydroxy, halogen, C(═O)OR 25a , and combinations thereof, 
 R 22a  and R 23a  are each present or absent, valency permitting, and each R 22a  and R 23a  present is independently selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 1 -C 6  alkoxy, hydroxy, and combinations thereof, 
 R 24a  is selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 6 -C 12  aryl, and combinations thereof, and 
 R 25a  is selected from the group consisting of hydrogen, deuterium, and C 1 -C 6  alkyl. 
 
     
     
       8. The method of  claim 7 , wherein the cyclopentaoxasilinone or cyclopentaoxaborininone of Formula (IIa) comprises a greater amount of one diastereomer of Formula (IIa) over other diastereomers of Formula (IIa). 
     
     
       9. The method of  claim 1 , wherein the cyclopentaoxaborininone of Formula (II) is a cyclopentaoxaborininone of Formula (IIb) 
       
         
           
           
               
               
           
         
       
       wherein
 R 20b  and R 21b  are each independently selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, hydroxy, halogen, C 1 -C 6  alkoxy, nitrile, C 6 -C 12  aryloxy, C 6 -C 12  aryl, C 4 -C 10  heteroaryl, trialkylsilane, hydroxy, halogen, nitrile, C(═O)OR 24b , and combinations thereof; 
 R 22b  is selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 6 -C 12  aryl, and combinations thereof; 
 R 23b  is selected from the group consisting of hydrogen, deuterium, C 1 -C 6  alkyl, C 1 -C 6  alkenyl, C 1 -C 6  alkoxy, hydroxy, and combinations thereof, and 
 R 24b  is selected from the group consisting of hydrogen, deuterium, and C 1 -C 6  alkyl. 
 
     
     
       10. The method of  claim 9 , wherein the cyclopentaoxaborininone of Formula (IIb) comprises a greater amount of one diastereomer of Formula (IIb) over other diastereomers of Formula (IIb). 
     
     
       11. The method of  claim 7 , wherein the cyclopentaoxasilinone is selected from the group consisting of 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       and combinations thereof,
 wherein i-Pr is isopropyl, TMS is trimethylsilyl, MOM is methoxymethyl acetyl and Me is methyl. 
 
     
     
       12. The method of  claim 1 , wherein the method further comprises the step of reacting the cyclopentaoxasilinone or cyclopentaoxaborininone with one or more additional reagents which oxidize, epoxidize, or reduce the cyclopentaoxasilinone or cyclopentaoxaborininone. 
     
     
       13. The method of  claim 12 , wherein the cyclopentaoxasilinone or cyclopentaoxaborininone is oxidized to form a cyclopentenone. 
     
     
       14. The method of  claim 1 , wherein the step contacting a siloxy-tethered 1,7-enyne with a thioether promoter further comprises the step of contacting the siloxy-tethered 1,7-enyne with carbon monoxide. 
     
     
       15. The method of  claim 14 , wherein the step of contacting a siloxy-tethered 1,7-enyne with a thioether promoter is preceeded by the step of contacting the siloxy-tethered 1,7-enyne with dicobalt octacarbonyl.